Herbicidal composition and method



United States Patent HERBICIDAL COMPOSITION AND METHOD Donald S. Acker,Waynesboro, Va., assignor to E. 1. du

Pont de Nemours and Company, Wilmington, DeL, a 5

corporation of Delaware N0 Drawing. Original application Aug. 17, 1960,Ser. No.

50,072. Divided and this application Sept. 25, 1962,

Ser. No. 226,164

2 Claims. (CI. 71-25) This application isa divisional application ofcopending application Serial No. 50,072, filed August 17, 1960, which inturn is a continuation-in-part of the copending application Serial No.646,541, filed March 18, 1957, both now abandoned. i

This invention relates to2-chloro-4,6-bis-(alkoxypropylamino)-s-triazines and to herbicidalcompositions and methods employing these compounds.

I have found that the substituted symmetrical triazines represented bythe following formula possess outstanding herbicidal activity:

The substituted triazines according to this invention where R and R aredifferent can be prepared by thereaction of cyanuric chloride with onemolecular equivalent of an amine of the formula H N(CH --OR, in ac- I,cordance with the following equation:

followed by reaction with one molecular equivalent of an amine of theformula H N(CH -OR, as follows:

According to an alternative method of preparing theunsymmetricaltriazines of this invention, eyanuric chloride is reactedwith a mixture of equimolecular amounts of the two amines H N (CH OR andaccording to Reaction Equation. 2 above. a

The product of this reaction is. isolated by neutralization with aqueousalkali followed by cooling of thereaction mixture, bringing aboutprecipitation of the product which can then be recovered by simplefiltration. If desired, the product can be recrystallized from commonorganic solvents, preferably polar solvents such as dioxane,dirnethylformamide, water, dimethylsulfoxide, and acetone orcombinations thereof, giving a high purity product.

These compounds are in most instances crystalline solids that arerelatively insoluble in waterv As aforementioned, the compounds ofFormula 1 are characterized by outstanding herbicidal activity. Whenapplied at appropriate dosages, they are effective in controlling bothbroadleaf weeds and grasses. They can be used as soil sterilants andalso as postand pie-emergence herbicides.

In use these compounds can be applied to areas to be protected fromundesirable vegetation in any of a variety of compositions. Thus anythat are sutficiently watersoluble can be applied simply as watersolutions.

It is preferred, however, that the compounds be extended with a carriermaterial or conditioning agent of the kind used and commonly referred toin the art'as a herbicidal adjuvant or modifier. Such adjuvants areinert solids, surface active agents and organic liquids.

The compounds shown above will be included in such compositions insufficient amount so that they-can exert a herbicidal effect. Usuallyfrom about 1 to by weight of the compounds are included in suchformulations.

Powder formulations can be prepared with inert solids. The formulationsthus can be prepared with inert solids to form dusts, or suspended in asuitable liquid medium for spray application. The powders usuallycomprise active ingredient admixed with minor amounts of conditioningagent. Natural clays (either absorptive such as attapulgite orrelatively non-absorptive such as china clays), diatomaceous earth,walnut shell flour, redwood flour, synthetic fine silica, calciumsilicate and other inert solid carriers of the kind conventionallyemployed in powder fungicidal compositions can be used. The activeingredient usually makes up from about 25-90% of these powdercompositions. The solids ordinarily should be very finely divided andshould have a particle size below about 50 microns and preferably belowabout 20 microns. For conversion of the powders to dusts, talc,pyrophyllite, tobacco dust, volcanic ash and other dense, rapid-settlinginert solids customarily are used.

If the active compound is water soluble, it can be sprayed or in anyother desired manner applied to an absorptive powder which can then bedried to produce a dry product. Any of the above absorptive materialscan be used for the preparation of such products.

Liquid compositions including the active compounds above described canbe prepared by admixing the compound With a suitable liquid diluentmedium. The active compound can be either in solution or in suspensionin the liquid medium. Typical of the liquid media com monly employed arekerosene, Stoddard solvent, xylene, alcohols, alkylated naphthalene,diesel oil, glycols and ketones such as diisobutyl ketone,cyclohexanone, etc. The active ingredient usually makes up from about0.5 to 50% of these liquid compositions. Some of these compositions aredesigned to be used as such, and others to be extended with largequantities of water.

Compositions in the form of wettable powders or liquids can also includeone or more surface-active agents such as wetting, dispersing oremulsifying agents. Thus mixtures of the above liquids with the activecompounds can contain an emulsifying agent to make an emulsifiable oilcomposition. The surface-active agents cause the compositions todisperse or emulsify easily in water to give aqueous sprays.

The surface-active agents employed can be of the anionic, cationic ornonionic type. They include, for example, sodium oleate, sulfonatedpetroleum oils, alkyl aryl sulfonates, sodium lauryl sulfate,polyethylene oxides, lignin sulfonates, and other surface active agents.A detailed list of such agents is set forth in an article by McCutcheonin Soap and Chemical Specialties, volume 31, No. 7, pages 50-61; No. 8,pages 48-61; No. 9, pages 52-67; and No. 10, pages 48-67 (1955).

The compounds can be applied in compositions of the types shown in JonesUS. Patent 2,412,510 in which an active compound of the inventionreplaces the active materials of that patent in the composition shownand in like amounts. Similarly, any of the carriers, additives orsurface-active agents there named or referred to can be used.

The herbicidal method of the present invention comprises applying asubstituted triazine of Formula 1, ordinarily in a herbicidalcomposition of the aforementioned type, to the locus or area to beprotected from undesirable plant growth. The active compound is, ofcourse, applied in sufficient amount to exert the desired herbicidalaction. The aplication can be made directly upon the locus or area andthe vegetation thereon during the period of infestation. Alternatively,the application can be made in advance of an anticipated weedinfestation.

The dosage employed can be determined readily by those skilled in theart by conventional techniques. It is, of course, dependent upon theparticular active ingredient employed, the nature of the formulationused, the type of treatment, the type of vegetation to be controlled,climatic conditions and the like. In general, complete control ofvegetation is obtained at rates of about 10 to 30 pounds per acre of theactive ingredient. Application at rates of about 0.5 to 5 pounds peracre of the active ingredient for pre-emergence or early directedpost-emergence treatment gives excellent control of broadleaf weeds andgrasses such as mustard, pigweed, lambsquarters, chickweed, velvetleaf,crabgrass, millet, ryegrass, foxtail, barnyard grass and cheat, in cropplants such as corn, cotton and sorghum. When applied to establishedperennial grasses at rates of about 0.5 to 2.0 pounds per acre, goodcontrol of germinating broadleaf weeds and crabgrass is obtained withminimum injury to the mature grasses.

In order that the invention can be better understood, the followingexamples are given in addition to those set forth above:

EXAMPLE 1 A freshly prepared slurry of 0.1 mole of cyanuric chloride inaqueous dioxane is stirred at 0 to 5 C. while 0.2 mole of3-methoxypropylamine is added. The mixture is allowed to warm to roomtemperature and then treated with a solution of 8 grams of sodiumhydroxide in 25 ml. of water at such a rate that the solution remainsneutral or slightly alkaline to phenolphthalein. The temperature isallowed to rise to 40-45 C. The reaction mixture is cooled in ice, andthe precipitate is collected and dried in vacuo at C. Recrystallizationfrom dioxane gives 23.5 grams (81%) of 2-chloro-4,6-bis(3-methoxypropylamino)-s-triazine having a melting point of159163 C.

EXAMPLES 2-4 The products listed in the following table are prepared inaccordance with the procedure of Example 1 by replacing the amine ofExample 1 with the amine listed in the table.

A freshly prepared slurry of 0.1 mole of cyanuric chloride in aqueousdioxane is stirred at 0 to 5 C. while 0.1 mole of 3-methoxypropylamineis added. Then, a solution of 4 grams of sodium hydroxide in 15milliliters of water is added at 0-5 C., while stirring, at such a ratethat the solution remains neutral or slightly alkaline tophenolphthalein.

After the addition is complete, 0.1 mole of 3-propoxypropylamine isadded, and the temperature allowed to rise to between 30 and 50 C., say40 C., where a reasonable reaction rate can be maintained. A solution of4 grams of sodium hydroxide in 15 milliliters of water is added, withslurry, at such a rate that the solution remains neutral or slightlyalkaline to phenolphthalein. The reaction mixture is cooled in ice, andthe precipitate is collected and dried in vacuo at 100 C.Recrystallization from dioxane gives essentially pure 2-ch1oro-4-methoxypropylamino-6-propoxypropylamine-s-triazine.

The following compounds are also prepared in accordance with theprocedure of Example 5 by utilizing cyanuric chloride and theappropriate amines:

Example No.:

(6) 2 chloro-4-methoxypropylamino-6-ethoxypropylamino-s-triazine (7) 2chloro-4-methoxypropylamino-6-propoxypropylamino-s-triazine (8) 2chloro-4-methoxypropylamino-6-isopropoxypropylamino-s-triazine (9) 2chloro-4-ethoxypropylamino-6-propoxypropylamino-s-triazine (10) 2chloro-4-ethoxypropylamino-6-isopropoxypropylamino-s-triazine (11)2-chloro-4-propoxypropylamino 6 isopropoxypropylamino-s-triazine EXAMPLE12 (A) Percent 2-chloro-4,6-bis(methoxypropylarnino)-s-triazine 75Sodium alkyl naphthalene sulfonate 1.5 Low viscosity methyl cellulose0.25 Synthetic fine silica 23.25

This composition, when applied at the rate of 30 pounds per acre ofactive ingredient in 300 gallons of water, gives excellent control ofgrass and broadleaf weeds, including crabgrass, goose grass, barnyardgrass, yellow foxtail, pigweed, mustard, lambsquarters and ragweed. Goodweed control is obtained for an extended period of time.

Another portion 'of this formulation is applied at a rate of pounds peracre of active ingredient extended with 200 gallons of water to an areaheavily infested with quackgrass and Johnson grass. Excellent kill ofthe foliage is noted within 14 days after treatment.

Another portion of this composition is extended with water to give a 1%sprayable formulation of active ingredient. This is sprayed onto foliageof mature cotton until the foliage is wetted thoroughly. Excellentdefoliation of the cotton is obtained.

At the rate of 2 pounds of triazine per acre in 40 gallons of water,this composition gives good pre-emergence control of broadleaf weedssuch as mustard, pigweed and chickweed, and grass weeds such ascrabgrass, foxtail and Johnson grass, in newly seeded fields of corn andpeanuts, with no injury to the crops.

Percent 2-chloro-4,6-bis (ethoxypropylamino) -s-triazine 5 0 Sodiumlauryl sulfate 0.5 Sodium lignin sulfonate 1.0 Attapulgite clay 48.5

60 pounds of this formulation is extended with 200 gallons of water andapplied at the rate of 30 pounds per acre of active ingredient onto aweed infested area. Excellent weed control is obtained.

Percent 2-chloro-4,6-bis (propoxypropylamino)-s-triazine 75Polyoxyethylene esters of mixed fatty acids concreted with urea 2Synthetic calcium silicate 23 This composition can be dispersed ineither water or oil for application. When applied as a pre-emergencetreatment in 80 gallons of water per acre at the rate of 4 pounds of theactive ingredient per acre, excellent control of annual broadleaf andgrass weeds in corn and cotton is obtained. When applied at the rate of20 pounds of the active ingredient per acre in 100 gallons of dieseloil, excellent control of broadleaf and grass weeds is obtained.

Percent 2-chloro-4,6-bis(ethoxypropylamino)-s-triazine Oleyl ester ofsodium isethionate 1.0 Partially desulfonated sodium lignin sulfonate0.5 Diatomaceous silica 48.5

When applied at the rate of 30 pounds of active ingredient per acre in200 gallons of water to an area infested with both grasses and broadleafweeds, excellent weed control is obtained.

6 EXAMPLE 13 The following dust compositions are prepared by firstblending together the active material and the minor diluent and thenmicropulverizing. The resulting powder concentrate is then extended withthe major diluent in a second blending operation.

Percent 2-chloro-4,6-bis(propoxypropylamino)-s-triazine 10 Attapulgiteclay 10 Micaceous talc 2-chloro-4,6-bis(ethoxypropylamino)-s-triazine 20Diatomaceous silica 30 Pyrophyllite 502-chloro-4,6-bis(methoxypropylamino)-s-triazine 15 Kaolin clay 15Tobacco dust 70 2-chloro-4,6-bis(isopropoxypropylamino)-s-triazine 10Synthetic calcium silicate 10 Pulverized phosphate rock 80 Thesecompositions are applied with hand-dusting equipment at the rate of 25to 30 pounds of the active ingredient per acre to weed-infested areasusing standard dusting equipment. Good control of crabgrass, peppergrass, ragweed, lambsquarters and other weeds is thereby obtained.

This example is repeated, substituting the compounds of Examples 6through 11 for the triazines of this example, with equally excellentresults noted.

EXAMPLE 14 The following pellet compositions are prepared by firstblending and micropulverizing the components, then moistening with 1020%water followed by extrusion through orifices to produce compactedpellets.

Percent 2-chloro-4,6-bis (methoxypropylarnino)-s-triazine 5 Alkylnaphthalene sulfonate, Na salt 1 Anhydrous sodium sulfate 10 Hydratednon-swelling clay 84 2-chloro-4,6-bis (ethoxypropylamino)-s-triazine 25Sodium lignin sulfonate 10 Kaolin clay 652-chloro-4,6-bis(propoxypropylamino)-s-triazine l5 Bentonite clay(montmorillonite) 85 These formulations, when applied at the rate of 25to 30 pounds of the active ingredient per acre to undersirablevegetation including both broadleaf and grass weeds, give excellent weedcontrol.

EXAMPLE 15 The following powders are prepared in accordance with theprocedure of Example 12. They are intended primarily for dispersion inan oil medium for application from an oil suspension. However, they arealso dispersible in water and can be used in accordance with theprocedure of Example 12.

Percent 2-chloro-4,6-bis(methoxypropylamino)-s-triazine 50Polyoxyethylene esters of mixed fatty and resin acids blended with oilsoluble petroleum sulfonates 5 Attapulgite clay 452-chloro-4,6-bis(ethoxypropylamino)-s-triazine 75 Oil soluble petroleumsulfonate Diatomaceous silica 20 These compositions, when applied at therate of 25 pounds per acre of active ingredient after extension withdiesel oil to make a total application of 80 gallons of solution peracre, give excellent post-emergence control of heavy infestations ofgrass and broadleaf weeds, such as quackgrass, foxtail, crabgrass,black-eyed-susan, pigweed, and fiower-of-an-hour.

I claim:

1. The method for the control of weeds comprising applying to the locusto be treated, in a herbicidally effective amount, a compoundrepresented by the formula where R and R are alkyl of less than 4 carbonatoms.

2. A herbicidal composition comprising a surface active agent selectedfrom the group consisting of anionic, cationic and nonionic surfaceactive agents, and a herbicidal amount of a compound represented by theformula where R and R are alkyl of less than 4 carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 2,497,917 2/1950Stauffer 260249.8 X 20 2,891,855 6/1959 Gysin et al. 71-2.5 3,152,88210/1964 Luckenbough 7l2.6 X

LEWIS GOTTS, Primary Examiner.

JULIAN S. LEVITT, Examiner.

1. THE METHOD FOR THE CONTROL OF WEEDS COMPRISING APPLYING TO THE LOCUSTO BE TREATED, IN A HERBICIDALLY EFFECTIVE AMOUNT, A COMPOUNDREPRESENTED BY THE FORMULA